冷动力喷涂法制备钨和钨合金涂层 及其涂层的计算模拟

采用冷动力喷涂法以纯钨和钨-镍-铁合金为原料在铜合金基体上制备了钨涂层和钨-镍-铁涂层. 研究了冷喷涂过程中钨粉粒径、喷涂距离等因素对涂层性能的影响. 用扫描电子显微镜分析了涂层的表面、断面微观结构, 并用原子力显微镜测量了涂层的粗糙度. 此外, 计算了冷喷涂过程中粉末颗粒的实际速度, 并采用有限元分析软件ANSYS/LS-DYNA模拟了冷喷涂过程中颗粒撞击基体时的变形情况.     

Ion-implanted deuterium accumulation in a deposited tungsten coating

The effects of trapping of ion-implanted deuterium and its thermal desorption on the structure and stressed state of a tungsten coating deposited on a composite substrate is studied. The amount of accumulated deuterium, macrostresses of the coating, and the shape of thermal desorption spectra are shown to depend on the D⁺ ion fluence and the irradiation temperature. Possible mechanisms of these processes are proposed.     

Studies on the influence of surface pre-treatments on electroless copper coating of boron carbide particles

Boron carbide is one of the hard ceramic particles which find application as structural materials and neutron shielding material due to its high neutron capture cross section. Copper coating on boron carbide particle is essential for the synthesis of metal-ceramic composites with enhanced sinterability and dispersibility. Surface characteristics of the substrate and the coating parameters play a foremost role in the formation of effective electroless coating. The effect of surface pre-treatment conditions and pH on electroless copper coating of boron carbide particles has been studied. Surface pre-treatement of B₄C when compared to acid treated and alkali treated particles were carried out. Uniform copper coating was observed at pH 12 in alkali treated particles when compared to others due to the effective removal of inevitable impurities during the production and processing of commercially available B₄C. A threshold pH 11 was required for initiation of copper coating on boron carbide particles. The growth pattern of the copper coating also varies depending on the surface conditions from acicular to spherical morphology.     

Effect of pretreatment methods and chamber pressure on morphology, quality and adhesion of HFCVD diamond coating on cemented carbide inserts

In the present investigation, diamond coating was deposited on cemented carbide substrate by hot filament chemical vapour deposition. The effect of substrate pretreatment methods and chamber pressure on morphology, quality, and adhesion of the diamond film were studied. The carbide inserts were pretreated with acid, Murakami's solution, and Murakami's solution followed by acid, respectively. The chamber pressure was set at 6.6, 13.2, 26.4, 39.6 and 66 mbar. Deposition carried out at pressure of 26.4 and 39.6 mbar on inserts pretreated with acid exhibited uniform crystal habit and provided coating-substrate adhesion adequate for machining application. Good coating morphology was obtained when deposition was done at 6.6 mbar on carbide inserts treated with Murakami's solution. Pretreatment with Murakami's solution followed by acid and deposition at 6.6 mbar also resulted in good morphology of diamond film. Indentation (Rockwell C scale) was done on diamond-coated inserts to assess coating-substrate adhesion under three loads of 294, 588 and 980 N. The diameter of the indentation crack at the coating-substrate interface was observed under SEM. The results suggested that diamond coating deposited at medium pressure of 26.4 mbar on carbide substrate treated with acid not only exhibited best morphology but also highest coating-substrate adhesion and improved machining performance.     

B<Subscript>4</Subscript>C protective coating under irradiation by QSPA-T intensive plasma fluxes

The effect of the QSPA-T pulsed plasma irradiation on the crystalline boron carbide B₄C coating was examined. The duration of the rectangular plasma pulses was 0.5 ms with an interval of 5–10 min between pulses. The maximum power density in the central part of plasma stream was 1 GW/m². The coating thickness varied from 20 to 40 μm on different surface areas. Modification of the surface layers and transformation of the coating at elevated temperature under plasma pulse irradiation during four successive series of impulses are described. It is shown that the boron carbide coating withstood the full cycle of tests under irradiation with 100 plasma pulses with peak power density of 1GW/m². Constitutive surface deterioration was not detected and the boron carbide coating kept crystal structure B₄C throughout the irradiation zone at the surface depth no less 2 μm.     

Investigations of silicon nitride and boron carbide monolayers and Si<Subscript>3</Subscript>N<Subscript>4</Subscript>/B<Subscript>4</Subscript>C multilayers

Many different coating concepts for improving mechanical properties have been worked out. One of the advanced coating concepts is the multilayer and superlattice concept, mainly with one or two metallic components. Previous work has shown that the mechanical properties of the covalent-bonded Si₃N₄ and SiC could be improved when combining them in a multilayer system. In the present work the silicon nitride monolayer from the earlier work was combined with boron carbide instead of silicon carbide. First, the boron carbide thin films deposited at different substrate temperatures were examined. Then the number of monolayers in the multilayer system with a constant layer thickness was varied in order to investigate the influence of the interfaces on film properties of the multilayer system. PACS 81.05.Je; 81.15.Cd; 82.80.Pv; 87.64.Je     

反应等离子喷涂纳米TiN涂层的显微硬度及微观结构研究

阐述了反应等离子喷涂(RPS)方法的基本思想.利用气体隧道等离子喷枪，通过RPS方法在Q23 5钢基底上成功制备了氮化钛涂层.检测了TiN涂层在不同载荷下的显微硬度，结果显示TiN涂层具有明显的硬度压痕尺寸效应，在高载荷下加工硬化效应较弱.XRD,TEM及HRTEM等分析 表明,通过RPS方法制备得到了纳米TiN涂层，涂层由直径约为50—70nm的TiN晶粒及非晶Ti N所组成. 关键词： 反应等离子喷涂 纳米 氮化钛 微观结构     

Combustion synthesis of nano-sized tungsten carbide powder and effects of sodium halides

The synthesis of nano-size tungsten carbide powder has been investigated with a WO₃ + Mg + C + carbonate system using alkali halides. The effects of different types of alkali halides on combustion temperature and tungsten carbide formation were discussed. Sodium fluoride had a notable effect on the particle size of the product and the degree of transformation from the initial mixture. A small amount of ammonium carbonate activated the carburization of tungsten carbide by the gas phase carbon transportation. X-ray diffraction data and particle analysis showed that the final product synthesized from a WO₃–Mg–C–(NH₄)₂CO₃–NaF system contains pure-phase tungsten carbide with a particle size of 50–100 nm.     

TiN薄膜在纳米压痕和纳米划痕下的断裂行为

利用磁控溅射方法在Si(111)衬底上制备了具有(111)和(222)择优取向的TiN薄膜. 用纳米压痕和纳米划痕方法研究了该薄膜的变形和断裂行为. 用扫描电子显微镜、纳米压痕原位原子力显微镜及原位光学显微镜并结合加-卸载 曲线及划痕曲线获得了薄膜发生变形和断裂的微观信息. 在压痕试验中, TiN薄膜在压入深度为200 nm时表现为塑性变形及压痕周围的局部断裂, 随着压入深度的增大, 塑性变形和局部断裂变得越显著, 当最大压入深度达到临界值1000 nm时, 薄膜和衬底间发生了界面断裂. 在划痕实验中, 100 mN及200 mN的最大载荷均可以引起界面断裂. 最大为200 mN的载荷使得薄膜发生界面断裂的位置比用100 mN载荷时的位置提前, 但其临界断裂载荷和100 mN时及压痕实验时的临界界面断裂载荷基本相同. 关键词： TiN薄膜 纳米压痕 纳米划痕 界面断裂     

Co元素对硬质合金基底金刚石涂层膜基界面结合强度的影响

采用基于密度泛函理论的第一性原理平面波赝势方法, 研究了硬质合金刀具基底黏结相Co元素对金刚石涂层膜基界面结合强度的影响机理. 借助Materials Studio软件建立了WC/Diamond膜基界面模型和WC-Co/Diamond膜基界面模型, 采用CASTEP仿真软件计算了WC/Diamond膜基界面模型和WC-Co/Diamond膜基界面模型的最优稳定结构. 通过仿真计算, 获得了WC/Diamond膜基界面模型和WC-Co/Diamond膜基界面模型的界面结合能、电荷密度图及Mulliken重叠布居数. 经对比分析后发现, 硬质合金基底中磁性元素Co的存在能转移金刚石涂层膜基界面处W元素及C元素的电荷, 从而使膜基界面处的原子因失电荷而相斥, 这直接导致了金刚石涂层膜基界面间距变大, 使得金刚石涂层膜基界面结合能降低.     

Effect of active screen plasma nitriding pretreatment on wear behavior of TiN coating deposited by PACVD technique

Titanium based alloys are used extensively for improving wear properties of different parts due to their high hardness contents. Titanium nitride (TiN) is among these coatings which can be deposited on surface using various techniques such as CVD, PVD and PACVD. Their weak interface with substrate is one major drawback which can increase the total wear in spite of favorite wear behavior of TiN. Disc shaped samples from AISI H13 (DIN 1.2344) steel were prepared in this study. Single TiN coating was deposited on some of them while others have experienced a TiN deposition by active screen plasma nitriding (ASPN). Hardness at the surface and depth of samples was measured through Vickers micro hardness test which revealed 1810 Hv hardness as the maximum values for a dual-layered ASPN–TiN. Pin-on-disc wear test was done in order to study the wear mechanism. In this regard, the wear behavior of samples was investigated against pins from 100Cr6 (Din 1.3505) bearing steel and tungsten carbide–cobalt (WC–Co) steel. It was evidenced that the dual-layer ASPN–TiN coating has shown the least weight loss with the best wearing behavior because of its high hardness values, stable interface and acceptable resistance against peeling during wearing period.     

Synthesis of tungsten carbide nanopowder via submerged discharge method

Tungsten carbide nanopowder was prepared via pulsed discharge of bulk tungsten and graphite rods immersed in pure ethanol. The effect of discharge parameters on the characteristics of final products was investigated. Structural and morphological characterization of nanopowder was performed by means of X-ray diffraction analysis and transmission electron microscopy. In order to determine the feasibility of using synthesized material as an electrocatalyst, tungsten carbide nanopowder was tested for hydrogen evolution. A correlation was found between morphology of nanoparticles, their phase composition and electrocatalytic activity.     

高温高压下碳化钨晶体的结构、力学、电子、光学以及热力学性能的第一性原理计算

本文利用密度泛函理论中的广义梯度近似对碳化钨晶体的三种结构(碳化钨相、闪锌矿相以及纤锌矿相)进行了优化,得到能量最低的稳定构型,并在此基础上计算了它的力学、电子、光学和高温高压下的热力学性质.研究表明:在0～300 GPa压力范围内,碳化钨相具有最高的稳定性.同时,高压下碳化钨相的弹性常数满足Born-Huang准则,且0 GPa和300 GPa下的声子色散没有虚频,证明了高压下碳化钨相的静力学稳定性和动力学稳定性.电子性质表明了碳化钨的金属性.光学性质表明碳化钨在高能区很难吸收光.热力学性质的研究表明:体积比V/V_0对压强的变化更敏感;高温时C_V曲线近似一条直线;给定压强下热膨胀系数α在600 K温度以上增长非常缓慢;压强对德拜温度Θ_D的影响较大;在低压下格林艾森系数γ的变化较大.     

Mobilization of tungsten dust by electric forces and its bearing on tritiated particles in the ITER tokamak

Experimental investigations on the electric field strength required to overcome the adhesion forces of micron size tungsten metallic dust as well as silver and aluminum oxide in powdery form deposited on a conductive surface are presented. The results reveal a strong influence of particulate surface properties on the detachment threshold, especially for tungsten particles which exhibit a thin surface oxide layer that screens their electrical conductivity. Such tungsten particles makes possible that electrostatic self-charging occurs when tritiated because of their dielectric properties even if there are deposited on a conductive grounded surface.     

Theoretical and experimental investigation of X-ray O- and N-emission spectra of tungsten

The experimental investigation of the O_IIIN_{VI, VII}-emission spectrum of pure tungsten and tungsten in W₂C is carried out. The experimental data are compared with the theoretical calculation of the intensity in the O_IIIN_{VI, VII}-emission spectrum of tungsten. A good agreement is obtained between the theoretical and experimental spectra. The conclusion was drawn, that the earlier published experimental data on the O_IIIN_VI,VII- spectrum of tungsten referred to carbide of tungsten.     

Surface composition of prepared tungsten carbide and its catalytic activity

The surface composition and electronic structure of carburized tungsten trioxide, which is prepared by heating WO₃ in carbon monoxide atmosphere at 700°C, are investigated using X-ray photoelectron spectroscopy (XPS). The relationship between the surface composition and the catalytic activity for methanol electro-oxidation is clarified. The formation of tungsten carbide at the surface enhances the catalytic activity. On the other hand, the presence of free carbon or tungsten trioxide in the surface layer reduces the activity remarkably. It is also shown that, the higher the electronic density of states near the Fermi level, the higher the catalytic activity. Additionally, the catalytic behavior of tungsten carbide for methanol electro-oxidation is mentioned.     

用脉冲紫外激光预处理提高刀具的金刚石涂层的附着强度

 采用脉冲紫外激光（XeCl，308nm）表面消融预处理方法以硬质合金为衬底制备了金刚石涂层刀具。利用压痕法对涂层结合强度进行了测试，得到了最佳预处理工艺条件。采用碳化硅增强铝合金材料对制备的金刚石涂层刀具进行了实际切削性能实验。实验结果表明：脉冲紫外激光表面消融预处理方法的采用对刀具的金刚石薄膜涂层附着强度的提高有很大的帮助。     

H+辐照前后W涂层表面的XPS分析

对离子束混合技术在不锈钢基体上沉积的W膜进行了H+辐照前后的XPS分析,研究了H+辐照对W的结合能的影响.分析结果表明,沉积的W膜中除了单质钨外,还有部分钨的氧化物,H+辐照结果表明,H+的辐照使钨的结合能向低能方向偏移;钨的氧化物有所减少,说明污染的氧化物在一定程度上被择优溅射掉.     

碳化硼薄膜的激光法制备及性能

采用KrF准分子激光器,在Si,Ge光学衬底上制备了碳化硼薄膜,研究了不同激光能量、靶材与衬底距离、衬底负偏压等条件对薄膜性能的影响。利用傅里叶变换红外光谱仪（FT-IR）和纳米压痕仪,并依据光学薄膜测试的通用标准,对样品的光学透过率、纳米硬度及膜层与衬底的结合性能进行了测试。结果表明:Si,Ge衬底单面镀碳化硼薄膜后最高透过率提高10%以上,纳米硬度提高到未镀膜的3倍以上,且膜层与衬底有较好的结合性能,表明制备的碳化硼薄膜可对光学材料起到较好的增透保护作用。     

Electroless deposition of Ni-W-P coating on AZ91D magnesium alloy

Ternary Ni-W-P alloy coating was deposited directly on AZ91D magnesium alloy by using an alkaline-citrate-based baths. Nickel sulfate and sodium tungstate were used as metal ion sources, respectively, and sodium hypophosphite was used as a reducing agent. The pH value of the electroless bath was tailored for magnesium alloy. The coating was characterized for its structure, morphology, microhardness and the corrosion properties. SEM observation showed the presence of dense and coarse nodules in the ternary coating. EDS analysis showed that the content of tungsten in the Ni-W-P alloy was 4.5 wt.%. Both the electrochemical analysis and the immersion test in 10% HCl solution revealed that the ternary Ni-W-P coating exhibited good corrosion resistance properties in protecting the AZ91D magnesium alloy.